Internal resistance

Modern batteries

In 1989, Goodenough and Arumugam Manthiram of the University of Texas at Austin showed that cathodes containing polyanions, e.g., sulfates, produce higher voltages than oxides due to theinductive effect of the polyanion.

In 1991, Sony and Asahi Kasei released the first commercial lithium-ion battery.

In 1996, Goodenough, Akshaya Padhi and coworkers identified lithium iron phosphate (LiFePO4) and other phospho-olivines (lithium metal phosphates with the same structure as mineral olivine) as cathode materials.

In 2002, Yet-Ming Chiang and his group at MIT showed a substantial improvement in the performance of lithium batteries by boosting the material's conductivity by doping it with aluminium,niobium and zirconium. The exact mechanism causing the increase became the subject of widespread debate.

In 2004, Chiang again increased performance by utilizing iron phosphate particles of less than 100 nanometers in diameter. This decreased particle density almost one hundredfold, increased the cathode's surface area and improved capacity and performance. Commercialization led to a rapid growth in the market for higher capacity LIBs, as well as a patent infringement battle between Chiang and Goodenough.

As of 2011, lithium-ion batteries account for 66% of all portable secondary (i.e., rechargeable) battery sales in Japan.

Electrochemistry

The three participants in the electrochemical reactions in a lithium-ion battery are the positive and negative electrodes and the electrolyte.

Both electrodes are materials into which, and from which, lithium ions can migrate. During insertion (or intercalation) lithium ions move into the electrode. During the reverse process, extraction (ordeintercalation), lithium ions move back out. When a lithium-based cell is discharging, the positive lithium ion is extracted from the negative electrode (usually graphite) and inserted into the positive electrode (lithium containing compound). When the cell is charging, the reverse occurs.

Useful work can only be extracted if electrons flow through a closed external circuit. The following equations show one example of the chemistry, in units of moles, making it possible to use the coefficient .

The overall reaction has its limits. Overdischarge supersaturates lithium cobalt oxide, leading to the production of lithium oxide,possibly by the following irreversible reaction:

Overcharge up to 5.2 volts leads to the synthesis of cobalt(IV) oxide, as evidenced by x-ray diffraction

In a lithium-ion battery the lithium ions are transported to and from the cathode or anode, with the transition metal, cobalt (Co), in being oxidized from Co3+ to Co4+ during charging, and reduced from Co4+ to Co3+ during discharge.

The energy provided by the cell is equal to the voltage times the charge. Each gram of lithium represents Faraday's constant/6.941 or 13 901 coulombs. For a voltage of 3 V, this gives 41.7 kJ per gram of lithium, or 11.6 kWh per kg. This is a bit more than the heat of combustion of gasoline, but does not take into account all the other materials that go into a lithium battery and which make lithium batteries many times heavier per unit of energy.

Electrolytes

The cell voltages given in the Electrochemistry section are larger than the potential at which aqueous solutions can electrolyze, in addition lithium is highly reactive to water, therefore, nonaqueous or aprotic solutions are used.

Liquid electrolytes in lithium-ion batteries consist of lithium salts, such as LiPF6, LiBF4 or LiClO4 in an organic solvent, such as ethylene carbonate, dimethyl carbonate, and diethyl carbonate. A liquid electrolyte conducts lithium ions, acting as a carrier between the cathode and the anode when a battery passes an electric current through an external circuit. Typical conductivities of liquid electrolyte at room temperature (20 °C (68 °F)) are in the range of 10 mS/cm (1 S/m), increasing by approximately 30–40% at 40 °C (104 °F) and decreasing by a slightly smaller amount at 0 °C(32 °F)

Unfortunately, organic solvents easily decompose on anodes during charging. However, when appropriate organic solvents are used as the electrolyte, the solvent decomposes on initial charging and forms a solid layer called the solid electrolyte interphase (SEI), which is electrically insulating yet provides sufficient ionic conductivity. The interphase prevents decomposition of the electrolyte after the second charge. For example, ethylene carbonate is decomposed at a relatively high voltage, 0.7 V vs. lithium, and forms a dense and stable interface.

A good solution for the interface instability is the application of a new class of composite electrolytes based on POE (poly(oxyethylene)) developed by Syzdek et al. It can be either solid (high molecular weight) and be applied in dry Li-polymer cells, or liquid (low molecular weight) and be applied in regular Li-ion cells.

Advantages and disadvantages

Note that both advantages and disadvantages depend on the materials and design that make up the battery. This summary reflects older designs that use carbon anode, metal oxide cathodes, and lithium salt in an organic solvent for the electrolyte.

Advantages

A lithium-ion battery from a laptopcomputer (176 kJ)

· Wide variety of shapes and sizes efficiently fitting the devices they power.

· Much lighter than other energy-equivalent secondary batteries.

· High open circuit voltage in comparison to aqueous batteries (such as lead acid, nickel-metal hydride and nickel-cadmium). This is beneficial because it increases the amount of power that can be transferred at a lower current.

· No memory effect.

· Self-discharge rate of approximately 5–10% per month, compared to over 30% per month in common nickel metal hydride batteries, approximately 1.25% per month for Low Self-Discharge NiMH batteries and 10% per month in nickel-cadmium batteries. According to one manufacturer, lithium-ion cells (and, accordingly, "dumb" lithium-ion batteries) do not have any self-discharge in the usual meaning of this word. What looks like a self-discharge in these batteries is a permanent loss of capacity. On the other hand, "smart" lithium-ion batteries do self-discharge, due to the drain of the built-in voltage monitoring circuit.

· Components are environmentally safe as there is no free lithium metal.

Disadvantages

Cell life

· Charging forms deposits inside the electrolyte that inhibit ion transport. Over time, the cell's capacity diminishes. The increase in internal resistance reduces the cell's ability to deliver current. This problem is more pronounced in high-current applications. The decrease means that older batteries do not charge as much as new ones (charging time required decreases proportionally).

· High charge levels and elevated temperatures (whether from charging or ambient air) hasten capacity loss. Charging heat is caused by the carbon anode (typically replaced with lithium titanate which drastically reduces damage from charging, including expansion and other factors).

· A Standard (Cobalt) Li-ion cell that is full most of the time at 25 °C (77 °F) irreversibly loses approximately 20% capacity per year. Poor ventilation may increase temperatures, further shortening battery life. Loss rates vary by temperature: 6% loss at 0 °C (32 °F), 20% at 25 °C (77 °F), and 35% at 40 °C (104 °F). When stored at 40%–60% charge level, the capacity loss is reduced to 2%, 4%, and 15%, respectively. In contrast, the calendar life of LiFePO4 cells is not affected by being kept at a high state of charge.

Internal resistance

· The internal resistance of standard (Cobalt) lithium-ion batteries is high compared to both other rechargeable chemistries such as nickel-metal hydride and nickel-cadmium, and LiFePO4 and lithium-polymer cells. Internal resistance increases with both cycling and age. Rising internal resistance causes the voltage at the terminals to drop under load, which reduces the maximum current draw. Eventually increasing resistance means that the battery can no longer operate for an adequate period.

· To power larger devices, such as electric cars, connecting many small batteries in a parallel circuit is more effective and more efficient than connecting a single large battery.